The present invention relates to a concentrated aqueous hydroxylamine salt solution and a method for stably storing the concentrated aqueous hydroxylamine solution.
Processing of silver halide color photographic photosensitive materials is essentially comprised of two processes, color development and desilvering, and the desilvering is comprised of bleaching and fixing steps, or a bleach-fixing step. In addition thereto, such processes as rinsing and stabilizing may also be conducted.
A color developing solution employed in a color development process has been commonly comprised of a p-phenylenediamine type compound as a developing agent, a hydroxylamine salt or a sulfite salt as an antioxidant, and a carbonate as a buffering agent. The color developing solutions are divided into several parts and handled as concentrated solution kit forms, in order to be as light as possible in terms of transportation and storage. A kit part containing a hydroxylamine salt, when it is prepared as a concentrated solution, has problems of precipitated crystals in winter or while being stored or transported in highly northern regions and deterioration of storage quality in summer or while being stored or transported in tropical regions.
Heretofore, over the years, various techniques have been studied to improve the stability of hydroxylamine. For example, a method in which sodium ethylenediamine tetraacetate is added to a solution of a hydroxylamine salt as described in U.S. Pat. No. 3,145,082, a method in which sodium hydroxyalkylidene diphosphate is added to a solution of a hydroxylamine salt as described in U.S. Pat. No. 3,647,449, or a method in which mercaptothiazole is added to a solution of a hydroxylamine salt as described in JP-A 5-170723 (the term, JP-A refers to an unexamined and published Japanese Patent Application) has been proposed. However, these methods are aimed to improve storage stability, when a hydroxylamine salt solution is in an alkaline state, in a high temperature state, or in the presence of tiny amount of heavy metal ions such as an iron, copper or nickel ion, and no techniques which solve both problems of storage stability at low temperatures (precipitation) and of stability at high temperature storage, of a concentrated solution of a hydroxylamine salt, simultaneously, have been known.
It is preferred to handle a hydroxylamine solutions in as concentrated a state as possible, because the container can be quite small and the total weight of the solution can remain quite light, resulting in improved handling characteristics as well as lower cost in physical distribution.
Further, known as a similar constitution to the present invention is an anti-corrosive washing composition to eliminate residual materials of plasma etching by use of a hydroxylamine salt aqueous solution such as described in JP-A 2001-501649, and the concentration and pH of the hydroxylamine salt solution is partly in the same region as the present invention but the additives are different. In addition, a quaternary ammonium hydroxide which is a necessary constitutive condition of said patent (JP-A 2001-501649) exhibits no effect on stability at low temperatures and at high temperatures when it is employed in the present invention, and hence the constitution and purpose are different from the present invention.
Accordingly, it a first object of the present invention to provide a method, in which crystal precipitation from a concentrated aqueous hydroxylamine salt solution is minimized, even when stored at a relatively low temperature.
It is a second object of the invention to provide a method, in which a concentrated aqueous hydroxylamine solution is stably stored keeping its components in solution, even when stored at a relative high temperature.
It is a third object of the invention to provide an aqueous hydroxylamine salt-containing solution, which can be supplied in a concentrated form, thereby allowing its container to be smaller and the total weight to be lighter, leading to more suitability for handling and physical distribution, and a method for storing the aqueous hydroxylamine-containing solution.
As a result of extensive studies, the foregoing objects of the invention can be accomplished by the following constitution.
[Structure 1]
An aqueous solution comprising a hydroxylamine salt in an amount of 18 to 35 weight-%, wherein the aqueous solution further comprises at least one compound selected from the group consisting of amino polycarboxylic acids and compounds represented by the following Formulas [1] to [6] in an amount of 1 to 30 weight-%, and pH of the aqueous solution is within the range of from 2 to 6: 
wherein R1 through R7 each represent independently a hydrogen atom, xe2x80x94OH, xe2x80x94COOM, xe2x80x94PO3M2, xe2x80x94SO3M or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, in which M is a hydrogen atom or an alkali metal; n and m each represent 0 or 1, provided that both m and n are not 0 at the same time; 
wherein at least one of A through F represents a sulfonic acid group or a sulfonic acid ester group, and the others represent a hydrogen atom, a halogen atom, a hydroxyl group or a saturated or unsaturated alkyl group; 
wherein, at least one of G through N represents a sulfonic acid group or a sulfonic acid ester group, and the others represent a hydrogen atom, a halogen atom, a hydroxyl group or a saturated or unsaturated alkyl group;
R41xe2x80x94SO3Mxe2x80x83xe2x80x83Formula [4]
wherein R41 represents a substituted or unsubstituted, saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and M represents a hydrogen atom, or an alkali metal;
xe2x80x83HOxe2x80x94(A1xe2x80x94O)l1xe2x80x94(A2xe2x80x94O)l2xe2x80x94(A3xe2x80x94O)l3xe2x80x94Hxe2x80x83xe2x80x83Formula [5]
wherein A1, A2, and A3 each represent a substituted or unsubstituted, straight or branched chain alkylene group, which may be the same or different; l1, l2, and l3 each represent 0 or an integer of 1 to 500; 
wherein R1 represents a substituted or unsubstituted hydroxyalkyl group or a substituted or unsubstituted aminoalkyl group; and R2 and R3 each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted hydroxyalkyl group or a substituted or unsubstituted benzyl group, provided that R1 and R2, R2 and R3, R3 and R1, or R1, R2 and R3 may combine with each other to form a ring.
[Structure 2]
An aqueous solution comprising a hydroxylamine salt in an amount of 18 to 35 weight-%, wherein the aqueous solution further comprises at least one compound selected from the group consisting of sorbitan polyethylene oxides, derivatives of sorbitan polyethylene oxide and compounds represented by the following Formulas [7] or [8] in an amount of 0.1 to 10 weight-%, and pH of the aqueous solution is within the range of from 2 to 6:
Axe2x80x94Oxe2x80x94(B)mxe2x80x94(C)nxe2x80x94Xxe2x80x83xe2x80x83Formula [7]
wherein A represents a monovalent organic group or an aryl group substituted by an alkyl group having 1 to 35 carbon atoms or by an alkenyl group having 2 to 35 carbon atoms; B and C, which may be the same or different, each represents 
in which a, b and c each are 0, 1, 2 or 3, d is 0 or 1, and Y is a hydrogen atom or a hydroxyl group; m and n each represent an integer of 1 to 100; X represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group;
Axe2x80x94Oxe2x80x94(CH2CH2O)xe2x80x94SO3Mxe2x80x83xe2x80x83Formula [8]
wherein M represents an alkali metal, a hydrogen atom, an ammonium salt or an alkanolamine salt; n is an integer of 1 to 100; and A represents a monovalent organic group or an aryl group substituted by an alkyl group having 3 to 20 carbon atoms.
[Structure 3]
The aqueous solution of Structure 1, wherein the aqueous solution comprises at least one compound represented by Formula [1] in an amount of 1 to 30 weight-%.
[Structure 4]
The aqueous solution of Structure 1, wherein the aqueous solution comprises at least one amino polycarboxylic acid in an amount of 1 to 30 weight-%.
[Structure 5]
The aqueous solution of Structure 1, wherein the aqueous solution comprises at least one compound represented by Formula [2], [3] or [4] in an amount of 1 to 30 weight-%.
[Structure 6]
The aqueous solution of Structure 1, wherein the aqueous solution comprises at least one compound represented by Formula [5] or [6] in an amount of 1 to 30 weight-%.
[Structure 7]
The aqueous solution of Structure 1, wherein the aqueous solution comprises at least one compound selected from the group consisting the amino polycarboxylic acids and the compounds represented by Formula [1] to [6] in an amount of 3 to 20 weight-%.
[Structure 8]
The aqueous solution of Structure 2, wherein the aqueous solution comprises at least one compound selected from the group consisting of sorbitan polyethylene oxides, derivatives of sorbitan polyethylene oxide and compounds represented by the following Formulas [7] or [8] in an amount of 0.4 to 5 weight-%.
[Structure 9]
The aqueous solution of Structure 1, wherein pH of the aqueous solution is within the range of 2.5 to 4.5.
[Structure 10]
The aqueous solution of Structure 2, wherein pH of the aqueous solution is within the range of 2.5 to 4.5.
[Structure 11]
A storing method of an aqueous solution comprising a hydroxylamine salt in an amount of 18 to 35 weight-%, wherein the storing method comprises a step of storing the aqueous solution in an plastic container having an oxygen permeation coefficient at 20xc2x0 C. and 65% RH of not more than 40 ml/m2xc2x7atmxc2x7day, and wherein the aqueous solution further comprises at least one compound selected from the group consisting of amino polycarboxylic acids and compounds represented by the following Formulas [1] to [6] in an amount of 1 to 30 weight-%, and pH of the aqueous solution is within the range of from 2 to 6: 
wherein R1 through R7 each represent independently a hydrogen atom, xe2x80x94OH, xe2x80x94COOM, xe2x80x94PO3M2, xe2x80x94SO3M or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, in which M is a hydrogen atom or an alkali metal; n and m each represent 0 or 1, provided that both m and n are not 0 at the same time; 
wherein at least one of A through F represents a sulfonic acid group or a sulfonic acid ester group, and the others represent a hydrogen atom, a halogen atom, a hydroxyl group or a saturated or unsaturated alkyl group; 
wherein, at least one of G through N represents a sulfonic acid group or a sulfonic acid ester group, and the others represent a hydrogen atom, a halogen atom, a hydroxyl group or a saturated or unsaturated alkyl group;
R41xe2x80x94SO3Mxe2x80x83xe2x80x83Formula [4]
wherein R41 represents a substituted or unsubstituted, saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and M represents a hydrogen atom, or an alkali metal;
HOxe2x80x94(A1xe2x80x94O)l1xe2x80x94(A2xe2x80x94O)l2xe2x80x94(A3xe2x80x94O)l3xe2x80x94Hxe2x80x83xe2x80x83Formula [5]
wherein A1, A2, and A3 each represent a substituted or unsubstituted, straight or branched chain alkylene group, which may be the same or different; l1, l2, and l3 each represent 0 or an integer of 1 to 500; 
wherein R1 represents a substituted or unsubstituted hydroxyalkyl group or a substituted or unsubstituted aminoalkyl group; and R2 and R3 each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted hydroxyalkyl group or a substituted or unsubstituted benzyl group, provided that R1 and R2, R2 and R3, R3 and R1, or R1, R2 and R3 may combine with each other to form a ring.
[Structure 12]
A storing method of an aqueous solution comprising a hydroxylamine salt in an amount of 18 to 35 weight-%, wherein the storing method comprising a step of storing the aqueous solution in an plastic container having an oxygen permeation coefficient at 20xc2x0 C. and 65% RH of not more than 40 ml/m2xc2x7atmxc2x7day, and wherein the aqueous solution further comprises at least one compound selected from the group consisting of sorbitan polyethylene oxides, derivatives of sorbitan polyethylene oxide and compounds represented by the following Formulas [7] or [8] in an amount of 0.1 to 10 weight-%, and pH of the aqueous solution is within the range of from 2 to 6:
Axe2x80x94Oxe2x80x94(B)mxe2x80x94(C)nxe2x80x94Xxe2x80x83xe2x80x83Formula [7]
wherein A represents a monovalent organic group or an aryl group substituted by an alkyl group having 1 to 35 carbon atoms or by an alkenyl group having 2 to 35 carbon atoms; B and C, which may be the same or different, each represents 
in which a, b and c each are 0, 1, 2 or 3, d is 0 or 1, and Y is a hydrogen atom or a hydroxyl group; m and n each represent an integer of 1 to 100; X represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group;
Axe2x80x94Oxe2x80x94(CH2CH2O)nxe2x80x94SO3Mxe2x80x83xe2x80x83Formula [8]
wherein M represents an alkali metal, a hydrogen atom, an ammonium salt or an alkanolamine salt; n is an integer of 1 to 100; and A represents a monovalent organic group or an aryl group substituted by an alkyl group having 3 to 20 carbon atoms.
[Structure 13]
The storing method of Structure 11, wherein the plastic container is a flexible bag.
[Structure 14]
The storing method of Structure 12, wherein the plastic container is a flexible bag.
[Structure 15]
The storing method of claim 11, wherein the oxygen permeation coefficient of the plastic container is not more than 20 ml/m2xc2x7atmxc2x7day.
[Structure 16]
The storing method of Structure 12, wherein the oxygen permeation coefficient of the plastic container is not more than 20 ml/m2xc2x7atmxc2x7day.
The invention will be further concretely explained below.
In the present invention, it has been found that an aqueous hydroxylamine salt solution having a concentration of 18 to 35 weight %, containing specific compounds at a specific concentration range, and further having a pH within the range of 2 to 6 has surprisingly overcome the problems of storage stability of a hydroxyl amine concentrated solution at low temperatures (crystallization property) as well as the storage stability at high temperatures, leading to the constitution of the present invention.
Compounds represented by the general formula [I] will now be detailed: 
wherein, each of R1 to R7 represents independently a hydrogen atom, xe2x80x94OH, xe2x80x94COOM, xe2x80x94PO3M2, xe2x80x94SO3M, or, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. xe2x80x9cnxe2x80x9d and xe2x80x9cmxe2x80x9d represent 0 or 1 but both of them are not 0 at the same time.
In the general formula [I], the alkyl group preferably has 1 to 4 carbon atoms, which may be either of a straight chain or branched chain type and may also be substituted with a substituent. Preferable substituents include xe2x80x94OH, xe2x80x94COOM, xe2x80x94PO3M2, xe2x80x94SO3M and xe2x80x94NR8R9, in which R8 and R9 each represent independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. M represents a hydrogen atom or an alkali metal, and preferably an alkali metal; xe2x80x9cnxe2x80x9d and xe2x80x9cmxe2x80x9d represent 0 or 1, but both of them are not 0 at the same time. R1 to R9 each may be the same or different.
Preferable examples of the compounds represented by the general formula [I] will be listed below, however, the invention is not limited thereby. 
Next, aminopolycarboxylic acids will be detailed.
As the aminopolycarboxylic acids of the invention, compounds represented by the following general formulas A-I to A-IV are preferably employed: 
wherein A1 to A4, which may be the same or different represent a hydrogen atom, a hydroxyl group, xe2x80x94COOM, xe2x80x94PO3(M1)2, xe2x80x94CH2COOM2, xe2x80x94CH2OH or an alkyl group having 10 or less of carbon atoms, provided that at least one of A1 to A4 is xe2x80x94COOM, xe2x80x94PO3 (M1)2 or xe2x80x94CH2COOM2; M, M1 and M2 each represent a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group; 
wherein A11 to A14, which may be the same or different represent xe2x80x94CH2OH, xe2x80x94COOM3, or xe2x80x94PO3(M4)2; M3 and M4 each represent a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group; X represents an alkylene group having 2 to 6 carbon atoms, or xe2x80x94(B1O)nxe2x80x94B2xe2x80x94; xe2x80x9cnxe2x80x9d represents an integer from 1 to 8, and B1 and B2, which may be the same or different, represents an alkylene group having 1 to 5 carbon atoms. In aforementioned general formula [A-II], an alkylene groups represented by X includes such as an ethylene, propylene or butylene group. In xe2x80x94(B1O)nxe2x80x94B2xe2x80x94 represented by X, the alkylene group represented by B1 and B2 includes such as methylene, ethylene and trimethylene. These alkylene groups may be substituted with a lower alkyl group such as methyl or ethyl group, or a hydroxyl group; 
wherein each of R1 to R3 represents independently a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group; W represents a bivalent connecting group; L represents anyone of the following: 
wherein Y1 to Y3 each represent a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, X2 and X3 each represent an oxygen atom or a sulfur atom, and R4 to R8 each represent a hydrogen atom, an alkyl group or an aryl group.
An alkyl group represented by R1 to R3 includes straight chain, branched chain or cyclic alkyl groups having 1 to 10 carbon atoms, and specifically preferable is a methyl or ethyl group. As an aryl group represented by R1 to R3 is preferably a phenyl group. When R1 to R3 are alkyl groups or aryl groups, they may be provided with a substituent. The substituent for R1 to R3 include, for example, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, an acylamino group, a sulfonylamino group, an ureido group, an urethane group, an aryloxy group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a sulfonyl group, a sulfinyl group, a hydroxyl group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, a phosphono group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an acyloxy group, a carbonamide group, a sulfonamide group, nitro group, etc. and preferable are the substituents represented by the following: 
wherein Ra, Rb, Rc, Rd and Re represent a hydrogen atom, an alkyl group or an aryl group.
Next, the alkylene groups represented by Y1 to Y3 include, for example, a methylene group, an ethylene group and a propylene group, and the arylene groups include a phenylene group. The alkylene groups and arylene groups represented by Y1 to Y3 may be substituted by a substituent. As the substituents, those listed for R1 to R3 described above can be employed, and preferable are the following:
xe2x80x94OH
xe2x80x94COOH
xe2x80x94CH2COOM
xe2x80x94CH2OH
xe2x80x94CONH2 
xe2x80x94CH2CONH2 
xe2x80x94CONHCH3 
where M represents a hydrogen atom, an alkali metal or an ammonium group.
In the general formula [A-III] described above, the bivalent connecting groups represented by W preferably include an alkylene group having 2 to 8 carbon atoms (including a cyclohexylene group), an arylene group having 6 to 10 carbon atoms,
"Parenopenst"B1O"Parenclosest"nB2xe2x80x94
where B1 and B2 represent an alkylene group or an arylene group, and xe2x80x9cnxe2x80x9d represents 1 to 3; 
where Z represents a hydrogen atom, an unsubstituted or axe2x80x94xe2x80x94COOM, xe2x80x94SO3M, or xe2x80x94OH substituted alkyl group, and M represents a hydrogen atom, an alkali metal or an ammonium group, and combinations thereof. 
In the formula, R1 to R3, and, R6 to R9 each represent a hydrogen atom, an alkyl group or aryl group which may be substituted; R4 and R5 each represent a hydrogen atom, a halogen atom a cyano group, a nitro group, an acyl group, a sulfamoyl group, a carbamoyl group, an alkoxycarbonyl group, an allyloxycarbonyl group, a sulfonyl group, a sulfinyl group or an alkyl or aryl group which may be substituted, and R4 and R5 may combine to a 5-membered or 6-membered ring. xe2x80x9cAxe2x80x9d represents a carboxyl group, a phosphono group, a sulfo group, a hydroxyl group, including their alkali metal or ammonium salts. Y represents an alkylene group or an arylene group, which may be substituted by a substituent. xe2x80x9ctxe2x80x9d and xe2x80x9cuxe2x80x9d each represent independently 0 or 1.
Among compounds represented by the general formula [A-IV], the compounds represented by the following general formula [B-I] and [B-II] are preferable: 
wherein R1 and R2 each represent a hydrogen atom, an alkyl group or an aryl group, L1 to L4 each represent an alkylene group or an arylene group, and M1 and M2 each represent a hydrogen atom, an alkali metal, an ammonium group or an organic ammonium group, W represents a bivalent connecting group; 
wherein R1 to R4 each represent the same as defined in R1 and R2 of the general formula [B-I], and L1 to L4, and, M1, M2 and W also represent the same as those of the general formula [B-I].
Specific examples of aminopolycarboxylic acids relating to the invention will be listed below. 
As the aminopolycarboxylic acid relating to the invention, aminopolycarboxylic acids other than the compounds represented by the general formulas [A-I] to [A-IV] described above can be employed:
[Axe2x80x2-1] Ethylenediamine tetraacetic acid
[Axe2x80x2-2] Trans-1,2-cyclohexanediaminetetraacetic acid
[Axe2x80x2-3] Dihydroxyethyl glycine
[Axe2x80x2-4] Ethylenediaminetetrakismethylenephosphonic acid
[Axe2x80x2-5] Nitrotrismethylene phosphonic acid
[Axe2x80x2-6] Diethylenetriaminepentakismethylenephosphonic acid
[Axe2x80x2-7] Diethylenetriaminepentaacetic acid
[Axe2x80x2-8] Ethylenediaminediorthohydroxyphenylacetic acid
[Axe2x80x2-9] Hydroxyethylethylenediaminetriacetic acid
[Axe2x80x2-10] Ethylenediaminepropionic acid
[Axe2x80x2-11] Ethylenediaminediacetatic acid
[Axe2x80x2-12] Hydroxyethyliminodiacetic acid
[Axe2x80x2-13] Nitrilo triacetate
[Axe2x80x2-14] Nitrilotripropionic acid
[Axe2x80x2-15] Triethylenetetraminehexaacetic acid
[Axe2x80x2-16] Ethylenediaminetetrapropionic acid
[Axe2x80x2-17] 1,3-Propylenediaminetetraacetic acid
[Axe2x80x2-18] Glycoletherdiaminetetraacetic acid
Further, aminopolycarboxylic acids such as the exemplified compounds 1 to 71 described at pages 7 to 11 of JP-A 4-174432 (the term, JP-A refers to an unexamined and published Japanese Patent Application) and the exemplified compounds 1 to 36 described at pages 25 to 30 of JP-A 4-204533 can also be employed.
Next, the compounds represented by the general formula [2] and [3] described above will be detailed: 
wherein among A to F, at least one represents a sulfonic acid group or a sulfonic acid ester group, and the others represent a hydrogen atom, a halogen atom, a hydroxyl group, a saturated or unsaturated alkyl group; 
wherein among G to N, at least one represents a sulfonic acid group or a sulfonic acid ester group, and the others represent a hydrogen atom, a halogen atom, a hydroxyl group, a saturated or unsaturated alkyl group.
Next, compounds represented by the general formula [2] or general formula [3] employed in the invention represent the compounds in which a sulfonic acid group or a sulfonic acid ester group is bonded directly to an unsaturated conjugated-ring having aromaticity. The number of the sulfonic acid group or sulfonic acid ester group may be single or plural. The sulfonic acid group and sulfonic acid group include the salt thereof. The salts include salts of an alkali metal such as lithium, sodium or potassium, and an ammonium salt.
In general formula [2] or [3], saturated or unsaturated alkyl groups represented by A to F or G to N preferably have 1 to 10 carbon atoms. The carbon chain may be a straight chain type or a branched chain type.
Specific examples of the compounds represented by the general formula [2] or [3] are shown below, however, they are not limited thereto. Herein, all of these exemplified compounds are shown as sodium salts, however, the part of or all of sulfonic acids or sulfonic acid esters may be salts other than sodium, such as potassium or lithium salt. 

Next, compounds represented by the general formula [4] described above will be detailed:
R41xe2x80x94SO3Mxe2x80x83xe2x80x83General formula [4]
wherein R41 represents a substituted or unsubstituted, saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms; and M represents a hydrogen atom, or an alkali metal such as potassium, sodium or lithium. As the substituent for R41, a sulfonic acid group, a hydroxyl group, an amino group, a carbonic acid group, an alkoxy group, an alkyl group and an alkylene group are listed.
Next, among compounds represented by the general formula [4], specific example compounds preferably employed in the invention will be shown.
(4-1) Methanesulfonic acid
(4-2) Ethanesulfonic acid
(4-3) Sodium allylsulfonate
(4-4) n-Propanesulfonic acid
(4-5) iso-Propylsulfonic acid
(4-6) Vinylsulfonic acid
(4-7) Sodium n-hexanesulfonate
(4-8) Sodium n-octanesulfonate
(4-9) Sodium n-octane-1,8-disulfonate
(4-10) Potassium dodecylsulfonate
(4-11) Sodium 1-carboxy-n-octane-8-sulfonate
(4-12) Sodium 2-methyl-2-propene-1-sulfonate
Next, compounds represented by the general formula [5] described above will be detailed:
HOxe2x80x94(A1xe2x80x94O)l1xe2x80x94(A2xe2x80x94O)l2xe2x80x94(A3xe2x80x94O)l3xe2x80x94Hxe2x80x83xe2x80x83General formula [5]
wherein A1, A2, and A3 each represent a substituted or unsubstituted, straight chain or branched alkylene group, which may be the same or different; xe2x80x9cl1xe2x80x9d, xe2x80x9cl2xe2x80x9d, and xe2x80x9cl3xe2x80x9d each represent 0 or an integer from 1 to 500.
Further, as the substituents, a hydroxyl group, a carboxyl group, a sulfonyl group, an alkoxy group, a carbamoyl group and a sulfamoyl group are listed. Preferably employed are the compounds in which A1, A2, and A3 each are unsubstituted. And, most preferable are the compounds in which A1, A2, and A3 are xe2x80x94CH2CH2xe2x80x94 or xe2x80x94CH(CH3)xe2x80x94CH2xe2x80x94.
xe2x80x9cl1xe2x80x9d, xe2x80x9cl2xe2x80x9d, and xe2x80x9cl3xe2x80x9d each represent 0 or an integer from 1 to 500, provided that xe2x80x9cl1xe2x80x9d+xe2x80x9cl2xe2x80x9d+xe2x80x9cl3xe2x80x9dxe2x89xa71.
Further, when the compounds represented by the general formula [5] in the invention are copolymers obtained through copolymerization of, for example, two kinds of monomers, A and B; those having the following arrangements are also included:
xe2x80x94Axe2x80x94Bxe2x80x94Axe2x80x94Bxe2x80x94Axe2x80x94Bxe2x80x94Axe2x80x94Bxe2x80x94Axe2x80x94Bxe2x80x94,
xe2x80x94Axe2x80x94Axe2x80x94Bxe2x80x94Axe2x80x94Bxe2x80x94Bxe2x80x94Axe2x80x94Axe2x80x94Axe2x80x94Bxe2x80x94Axe2x80x94Axe2x80x94Bxe2x80x94Bxe2x80x94Axe2x80x94, and
xe2x80x94Axe2x80x94Axe2x80x94Axe2x80x94Axe2x80x94Axe2x80x94Axe2x80x94Bxe2x80x94Bxe2x80x94Bxe2x80x94Bxe2x80x94Bxe2x80x94Bxe2x80x94Axe2x80x94Axe2x80x94Axe2x80x94Axe2x80x94Axe2x80x94.
Among these copolymers, specifically preferable compounds are block-polymers (Pluronic type nonion) of ethylene glycol and propylene glycol represented by the following general formula [5xe2x80x2]:
xe2x80x83HOxe2x80x94(CH2CH2xe2x80x94O)l4xe2x80x94(CH(CH3)CH2xe2x80x94O)l5xe2x80x94(CH2CH2xe2x80x94O)l6xe2x80x94Hxe2x80x83xe2x80x83General formula [5xe2x80x2]
wherein xe2x80x9cl4xe2x80x9d, xe2x80x9cl5xe2x80x9d, and xe2x80x9cl6xe2x80x9d are the same as defined in xe2x80x9cl1xe2x80x9d, xe2x80x9cl2xe2x80x9d, and xe2x80x9cl3xe2x80x9d in the general formula [5] described above.
In the compounds represented by the general formula [5xe2x80x2] of the invention, the content of ethyleneoxide (weight %) is preferably not less than 70 weight %, and specifically preferably not less than 80 weight, based on the total molecular weight.
Preferable specific examples of the compounds represented by the general formula [5] described above are as follows: 
Further, specific compounds represented by the general formulas [5] and [5xe2x80x2] are shown below:
HOxe2x80x94(CH2xe2x80x94CH2xe2x80x94O)axe2x80x2xe2x80x94(CH(CH3)xe2x80x94CH2xe2x80x94O)bxe2x80x2xe2x80x94(CH2xe2x80x94CH2xe2x80x94O)cxe2x80x2xe2x80x94H
In the compounds represented by the general formulas [5] and [5xe2x80x2] of the invention, polyethylene glycol (being also referred to as PEG) is most preferable.
In the case of the compound being polyethylene glycol, its average molecular weight is preferably within a range of from 2000 to 20000, and specifically preferably within a range of from 3000 to 15000.
Herein, the average molecular weight in the invention is a molecular weight calculated according to a hydroxyl value.
The compounds represented by the general formula [5] described above may be employed alone or in combinations of two or more kinds thereof.
Next, the compounds represented by the general formula [6] described above will be detailed: 
wherein R1 represents a substituted or unsubstituted hydroxyalkyl group or an substituted or unsubstituted aminoalkyl group; and R2 and R3 each represent a hydrogen atom, an alkyl group, a hydroxyalkyl group or a benzyl group, provided that R1 and R2, R2 and R3, R3 and R1, or, R1, R2 and R3 each may form a ring.
In the general formula [6], R1 represents a hydroxyalkyl group or aminoalkyl group, which may be substituted, the number of carbon atoms of the hydroxyalkyl group and aminoalkyl group being preferably 1 to 10, and more preferably 2 to 6. Examples of the substituent include a hydroxyl group, a carboxyl group, a carbonyl group, a sulfo group, a phosphono group, an ammonium group, a nitro group, an amino group and a halogen atom. R2 and R3 each include a hydrogen atom, an alkyl group which may be substituted and a benzyl group which may be substituted, and preferable are a hydrogen atom or a straight or branched alkyl group having 1 to 10 carbon atoms, which may be substituted by a substituent.
Examples of the substituent include a hydroxyl group, a carboxyl group, an alkoxycarbonyl group, an acylamino group, a carbamoyl group, an ureido group, an acyl group, a cyano group, a nitro group, an amino group, a sulfo group, an alkylsulfonyl group, an alkylsulfonylamino group, an arylsulfonyl group, an arylsulfonylamino group, a phosphono group, a phosphonic acid ester residual group, and a halogen atom. Preferable are a hydroxyl group, a carboxyl group, an alkoxycarbonyl group, a carbamoyl group and an amino group, and these may be further substituted by a hydroxyl, carboxyl sulfo or amino group.
R1 and R2, R2 and R3, R3 and R1, or, R1, R2 and R3 each may bond together with each other to form a ring.
The preferable specific examples of the compounds represented by the general formula [6] described above are shown below but are not limited thereto.
(6-1) Ethanolamine
(6-2) Diethanolamine
(6-3) Triethanolamine
(6-4) Di-isopropanolamine
(6-5) 2-Methylaminoethanol
(6-6) 2-Ethylaminoethanol
(6-7) 2-Dimethylaminoethanol
(6-8) 2-Diethylaminoethanol
(6-9) 1-Diethylamino-2-propanol
(6-10) 3-Diethylamino-1-propanol
(6-11) 3-Dimethylamino-1-propanol
(6-12) Isopropylaminoethanol
(6-13) 3-Amino-1-propanol
(6-14) 2-Amino-2-methyl-1,3-propanediol
(6-15) Ethylenediamine tetraisopropanol
(6-16) Benzylethanolamine
(6-17) 2-Amino-2-(hydroxymethyl)-1,3-propanediol
(6-18) 1,3-Diaminopropanol
(6-19) 1,3-Bis(2-hydroxyethylmethylamino)-propanol
(6-20) Triisopropanolamine
The compounds represented by the general formula [7] and the general formula [8], described above, will be detailed.
Axe2x80x94Oxe2x80x94(B)mxe2x80x94(C)nxe2x80x94Xxe2x80x83xe2x80x83General formula [7]
Axe2x80x94Oxe2x80x94(CH2CH2O)nxe2x80x94SO3Mxe2x80x83xe2x80x83General formula [8]
In the general formula [7], xe2x80x9cAxe2x80x9d represents a monovalent organic group, for example, an alkyl group having 6 to 50 carbon atoms, preferably 6 to 35 carbon atoms (such as hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl); or an aryl group substituted by an alkyl group having 1 to 35 carbon atoms, or by an alkenyl group having 2 to 35 carbon atoms. The preferable substituents on the aryl group include an alkyl group having 1 to 18 carbon atoms (for example, an unsubstituted alkyl group such as methyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl), a substituted alkyl group such as benzyl and phenetyl, or an alkenyl group having 2 to 20 carbon atoms (for example, an unsubstituted alkenyl group such as an oleyl, cetyl and allyl group).
As the aryl group, a phenyl, biphenyl or naphtyl group is listed, and preferable is a phenyl group. The substituting position on the aryl group may be any of ortho, metha and para, and plural groups can substitute. B and C respectively represent, 
and these may be the same or different, in which xe2x80x9caxe2x80x9d, xe2x80x9cbxe2x80x9d and xe2x80x9ccxe2x80x9d each are 0, 1, 2 or 3, xe2x80x9cdxe2x80x9d is 0 or 1, and Y is a hydrogen atom or a hydroxyl group); xe2x80x9cmxe2x80x9d and xe2x80x9cnxe2x80x9d represent an integer from 1 to 100. X is a hydrogen atom, an alkyl group, an alalkyl group or an aryl group, and includes, for example, the groups explained in xe2x80x9cAxe2x80x9d.
In the general formula [8], M represents an alkali metal (for example, Na, K, Li, etc.), a hydrogen atom, an ammonium salt or an alkanolamine salt, xe2x80x9cnxe2x80x9d is an integer from 1 to 100, and xe2x80x9cAxe2x80x9d represents a monovalent organic group, for example, an alkyl group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms (such as hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl); or an aryl group substituted by an alkyl group having 3 to 20 carbon atoms, and the preferable substituents include an alkyl group having 3 to 12 carbon atoms (for example, such as a propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl group).
As the aryl group, a phenyl, tolyl, xylyl, biphenyl or naphtyl group is listed, and preferable is a phenyl group or a tolyl group. The position of the aryl group at which an alkyl group bonds may be any of ortho, meta and para positions.
Examples of the compounds represented by the general formulas [7] and [8] are listed below, however, they are not limited thereby. 
Among the exemplified compounds described above, compounds 7-23, 7-28, 7-31, 7-32, 7-33, 7-34, 7-36, 7-37, 7-47, 8-8 and 8-9 are preferable.
Next, the polyethyleneoxide sorbitan and derivatives thereof described above will be detailed.
Polyethyleneoxide sorbitan and derivatives thereof used in the invention refer to compounds in which polyethyleneoxide is added to sorbitan and compounds derived from the polyethylene oxide sorbitan. As the derivative of polyethyleneoxide sorbitan, a sorbitan fatty acid ester can be exemplified. Such materials are commercially available, and include, for example, polyoxyethylene sorbitan monoolate (Product name: Nonion OT-221, manufactured by NIPPON YUSHI Co., Ltd.) and TWEEN80, manufactured by ICI Co.
The compounds represented by the general formulas [1] to [6] and aminopolycarboxylic acids described above are employed in an amount of 1 to 30 weight %, and more remarkable effect of the invention is performed when they are employed in an amount of from 3 to 20 weight %. Further, the compounds represented by the general formula [7] or [8], polyethyleneoxide sorbitan or derivatives thereof are employed in an amount of 0.2 to 10 weight %, and more remarkable effect of the invention is performed when they are employed in an amount of 0.4 to 5 weight %.
Further, the hydroxylamine salt aqueous solution according to the invention is employed at a pH of from 2 to 6, and more preferably within a pH range of from 2.5 to 4.5 to achieve more remarkable effect of the invention.
The hydroxylamine salts relating to the invention refers to salts of an inorganic or organic acid and a hydroxylamine, such as hydroxylamine sulfate, hydroxylamine nitrate, hydroxylamine phosphate, hydroxylamine oxalate, hydroxylamine citrate or hydroxylamine chlorate.
In the invention, by storing a hydroxylamine salt solution in a plastic container having an oxygen permeation coefficient of not more than 40 ml/m2xc2x7atmxc2x7day (at a temperature of 20xc2x0 C. and a relative humidity of 65%), and more preferably of not more than 20 ml/m2xc2x7atmxc2x7day, the effect of the invention is more remarkably performed.
The oxygen permeation coefficient of plastic container in the invention can be determined by the method described in xe2x80x9cO2 permeation of plasticcontainer, Modern Packing; N.J.Calyay, 1968xe2x80x9d Dec. issue, pages 143 to 145.
As plastic package material forming the containers, there can be employed in the invention, for example, a sheet comprised of plastic having a small oxygen permeation coefficient such as polyvinylidene chloride, nylon, saponified copolymer of ethylene-vinyl acetate, polyvinyl alcohol, polyvinyl chloride; a sheet in which a metal foil such as aluminum is laminated thereto or metal such as aluminum is evaporated thereto; or a laminated sheet in which a sheet comprised of polyethylene or an ethylene-vinyl acetate copolymer is pasted up further thereto. Further, these sheets may be employed alone or in combinations of plural sheets to form containers.
Of these plastic package materials, specifically preferably employed is polyvinylidene chloride, nylon or a saponified ethylene-vinyl acetate copolymer, in terms of minimized oxygen permeation coefficient, enhanced strength in the container form, and easy convertibility to containers.
The form of the container is not specifically limited, including, for example, a bottle type, a cubic type, a pillow type, etc. For example, to obtain a cubic type container, the plastic materials described above may concurrently be extruded to be formed into a laminated material. Specifically preferable is a flexible pillow type container, in terms of compactness and easy handling.
When the outer wall of a container is constituted by one sheet, an oxygen permeability coefficient of the sheet is not more than 40 ml/m2xc2x7atmxc2x7day as described above preferably, however, when the outer wall of a container is constituted by two sheets, it will do that an oxygen permeation coefficient of the total of said two sheets as a whole is not more than 40 ml/m2xc2x7atmxc2x7day. As the sheet constituting said outer wall can be employed a single-layered plastic sheet or a multi-layered plastic sheet in which plural plastic sheets are pasted up together. Further, the plastic sheet may be a sheet comprised of a plastic sheet alone, a sheet which is laminated with such as a metal foil or paper, or a sheet comprised of a plastic sheet provided with an evaporated metal film.
The single-layered plastic sheet includes, for example, a plastic sheet comprised of such as polyvinylidene chloride, nylon, a saponified ethylene-vinyl acetate copolymer, polyvinyl alcohol or polyvinylidene chloride; a sheet in which a metal foil comprised of such as aluminum, or paper is laminated thereto; or a sheet in which metal such as aluminum is evaporated onto the plastic sheet described above. The multi-layer sheet in which plural plastic sheets are pasted up together includes, for example, a 3-layer lamination of polyethylene terephthalate/polyvinyl alcohol.ethylene copolymer/polyethylene, a 3-layer lamination of stretched polypropylene/polyvinyl alcohol.ethylene copolymer/polyethylene, a 3-layer lamination of unstretched polypropylene/polyvinyl alcohol.ethylene copolymer/polyethylene, a 3-layer lamination of nylon/aluminum foil/polyethylene, a 3-layer lamination of polyethylene terephthalate/aluminum foil/polyethylene, a 4-layer lamination of cellophane/polyethylene/aluminum foil/polyethylene, a 3-layer lamination of aluminum foil/paper/polyethylene, a 4-layer lamination of polyethylene terephthalate/polyethylene/aluminum foil/polyethylene, a 4-layer lamination of nylon/polyethylene/aluminum foil/polyethylene, a 4-layer lamination of paper/polyethylene/aluminum foil/polyethylene, a 4-layer lamination of polyethylene terephthalate/aluminum foil/polyethylene terephthalate/polypropylene, a 4-layer lamination of polyethylene terephthalate/aluminum foil/polyethylene terephthalate/high density polyethylene, a 4-layer lamination of polyethylene terephthalate/aluminum foil/polyethylene/low density polyethylene, a 2-layer lamination of polyvinyl alcohol.ethylene copolymer/polypropylene, a 3-layer lamination of polyethylene terephthalate/aluminum foil/polypropylene, or a 3-layer lamination of paper/aluminum foil/polyethylene, and specifically preferably a 4-layer lamination of polyethylene/nylon coverd with polyvinylidene chloride/polyethylene/ethylvinyl acetate -polyethylene condensation product, a 3-layer lamination of polyethylene/nylon covered with polyvinylidene chloride/polyethylene, a 5-layer lamination of ethylvinyl acetate.polyethylene condensation product/polyethylene/aluminum evaporated nylon/polyethylene/ethylvinyl acetate.polyethylene condensation product, a 4-layer lamination of aluminum evaporated nylon/nylon/polyethylene/ethylvinyl acetate.polyethylene condensation product, a 3-layer lamination of stretched polypropylene/nylon coverd with polyvinylidene chloride/polyethylene, a 5-layer lamination of polyethylene/nylon covered with polyvinylidene chloride/polyethylene/nylon covered with polyvinylidene chloride/polyethylene, a 3-layer lamination of stretched polypropylene/polyvinylalcohol.ethylene copolymer/low density polyethylene, a 3-layer lamination of stretched polypropylene/polyvinylalcohol.ethylene copolymer/unstretched polypropylene, a 3-layer lamination of polyethylene terephthalate/polyvinylalcohol.ethylene copolymer/low density polyethylene or a 3-layer lamination of unstretched nylon/polyvinylalcohol.ethylene copolymer/low density polyethylene.
Further, in cases where the container is formed of a multi-layered plastic sheet, which is comprised of a plastic sheet having an oxygen permeability coefficient of not more than 40 ml/m2xc2x7atmxc2x7day being laminated with a plastic sheet comprised of, for example, polyethylene or an ethylene-vinyl acetate copolymer which have a large oxygen permeation coefficient but a high flexibility; containers exhibiting sufficient oxygen-impermeability as well as superior durability causing few pin holes can be obtained.
The thickness of a sheet forming the outer wall of containers varies depending on constitution material and cannot be defined unequivocally, however, preferable is approximately from 5 to 1500 xcexcm, and specifically preferably 10 to 500 xcexcm.